High charge density metallophosphate molecular sieves

ABSTRACT

A family of highly charged crystalline microporous metallophosphate molecular sieves designated PST-19 has been synthesized. These high charge density metallophosphates are represented by the empirical formula of: 
       R p+   r A +   m M 2+   x E y PO z    
     where A is an alkali metal such as potassium, R is an organoammonium cation such as tetraethylammonium, M is a divalent metal such as zinc and E is a trivalent framework element such as aluminum or gallium. The PST-19 family of materials are among the first MeAPO-type molecular sieves to be stabilized by combinations of alkali and quaternary ammonium cations, enabling unique compositions. The PST-19 family of molecular sieves has the SBS topology and catalytic properties for carrying out various hydrocarbon conversion processes and separation properties for separating at least one component.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Division of copending application Ser. No.15/586,503 filed May 4, 2017, which application claims priority fromApplication No. 62/341,190 filed May 25, 2016, now expired, the contentsof which cited applications are hereby incorporated by reference intheir entirety.

FIELD OF THE INVENTION

This invention relates to a family of high charge densitymetallophosphate-based molecular sieves designated PST-19. They arerepresented by the empirical formula of:

R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z)

where A is an alkali metal such as potassium, R is a quaternaryorganoammonium cation such as tetraethylammonium, M is a divalent metalsuch as zinc and E is a trivalent framework element such as aluminum orgallium. The PST-19 family of materials has the SBS topology and crystaldimensions on the order of a few microns or less.

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which aremicroporous and which are formed from corner sharing [AlO_(4/2)]⁻ andSiO_(4/2) tetrahedra. Numerous zeolites, both naturally occurring andsynthetically prepared are used in various industrial processes.Synthetic zeolites are prepared via hydrothermal synthesis employingsuitable sources of Si, Al and structure directing agents (SDAs) such asalkali metals, alkaline earth metals, amines, or organoammonium cations.The structure directing agents reside in the pores of the zeolite andare largely responsible for the particular structure that is ultimatelyformed. These species balance the framework charge associated withaluminum and can also serve as space fillers. Zeolites are characterizedby having pore openings of uniform dimensions, having a significant ionexchange capacity, and being capable of reversibly desorbing an adsorbedphase which is dispersed throughout the internal voids of the crystalwithout significantly displacing any atoms which make up the permanentzeolite crystal structure. Zeolites can be used as catalysts forhydrocarbon conversion reactions, which can take place on outsidesurfaces of the zeolite as well as on internal surfaces within the poresof the zeolite.

In 1982, Wilson et al. developed aluminophosphate molecular sieves, theso-called AlPOs, which are microporous materials that have many of thesame properties of zeolites, but are silica free, composed of[AlO_(4/2)]⁻ and [PO_(4/2)]³⁰ tetrahedra (See U.S. Pat. No. 4,319,440).Subsequently, charge was introduced to the neutral aluminophosphateframeworks via the substitution of SiO_(4/2) tetrahedra for [PO_(4/2)]⁺tetrahedra to produce the SAPO molecular sieves (See U.S. Pat. No.4,440,871). Another way to introduce framework charge to neutralaluminophosphates is to substitute [M²⁺O_(4/2)]²⁻ tetrahedra for[AlO_(4/2)]⁻ tetrahedra, which yield the MeAPO molecular sieves (seeU.S. Pat. No. 4,567,029). It is furthermore possible to introduceframework charge on AlPO-based molecular sieves via the introductionboth of SiO_(4/2) and [M²⁺O_(4/2)]²⁻ tetrahedra to the framework, givingMeAPSO molecular sieves (See U.S. Pat. No. 4,973,785).

In the early 1990's, high charge density molecular sieves, similar tothe MeAPOs but without the Al, were developed by Bedard (See U.S. Pat.No 5,126,120) and Gier (See U.S. Pat. No. 5,152,972). These metalphosphates (sometimes arsenates, vanadates) were based on M²⁺ (M=Zn,Co), the general formula of which, in terms of the T-atoms, T²⁺-T⁵⁺, wasapproximately A⁺T²⁺T⁵⁺O₄, having framework charge densities similar toSi/Al=1 zeolites and were charge balanced by alkali cations, A⁺, in thepores. Later attempts to prepare metallophosphates of similarcompositions but with organic SDAs led to porous, but interruptedstructures, i.e., the structures contained terminal P—O—H and Zn—N bonds(See J. Mater. Chem., 1992, 2 (11), 1127-1134.) Attempts at Alsubstitution in a zincophosphate network was carried out in the presenceof both alkali and organoammonium agents, specifically the most highlycharged organoammonium species, tetramethylammonium, but because of thehigh framework charge density, only the alkali made it into the pores tobalance framework charge (See U.S. Pat. No. 5,302,362). Similarly, in ahigh charge density zincophosphate system that yielded the zincphosphate analog of zeolite X, the synthesis in the presence of Na⁺ andTMA⁺ yielded a product that contained very little of the TMA⁺ (See Chem.Mater., 1991, 3, 27-29).

To bridge the rather large charge density gap between the MeAPOs of U.S.Pat. No. 4,567,029 and the aforementioned alkali-stabilizedMe²⁺-phosphates of Bedard and Gier, Stucky's group developed a synthesisroute using amines, often diamines, in ethylene glycol. They were ableto make high charge density, small pore MeAPOs in which theconcentrations of Co²⁺ and Al³⁺ in R(Co_(x)Al_(1-x))PO₄were varied suchthat 0.33≤x≤0.9 in the so-called ACP series of materials, the aluminumcobalt phosphates (See Nature, 1997, 388, 735). Continuing with thissynthesis methodology utilizing ethylene glycol-based reaction mixturesand matching the amines to framework charge densities for R(M²⁺_(x)Al_(1-x))PO₄, such that 0.4≤x≤0.5, (M²⁺=Mg²⁺, Mn²⁺, Zn²⁺, Co²⁺), thelarge pore materials UCSB-6, -8 and -10 were isolated (See Science,1997, 278, 2080). Similarly, this approach also yielded MeAPO analogs ofzeolite rho of the composition where RM²⁺ _(0.5)Al_(0.5)PO₄, whereR=N,N′-diisopropyl-1,3-propanediamine, M²⁺=Mg²⁺, Co²⁺ and Mn²⁺. Thereliance of this synthesis approach on an ethylene glycol solvent doesnot lend itself well to industrial scale, from both a safety andenvironmental point of view. While several others embraced Stucky'sapproach, there has been little activity in this intermediate chargedensity region, where 0.2≤x≤0.9 for the [M²⁺ _(x)Al_(1-x)PO₄]^(x−)compositions.

Pursuing aqueous chemistry, Wright et al. used highly chargedtriquaternary ammonium SDAs to make new MeAPO materials (See Chem.Mater., 1999, 11, 2456-2462). One of these materials, STA-5 with the BPHtopology, (Mg_(2.1)Al_(11.9)P₁₄O₂₈), exhibited significant substitutionof Mg' for Al³⁺, up to about 15%, but less substitution than seen inStucky's non-aqueous ethylene glycol approach.

More recently, Lewis et al. developed aqueous solution chemistry usingquaternary ammonium cations leading to high charge density SAPO, MeAPO,and MeAPSO materials, enabling greater substitution of SiO_(4/2) and[M²⁺O_(4/2)]²⁻ into the framework for [PO_(4/2)]⁺ and [AlO_(4/2)]⁻,respectively, using the ethyltrimethylammonium (ETMA⁺) anddiethyldimethylammonium (DEDMA⁺) SDAs. These materials include ZnAPO-57(U.S. Pat. No. 8,871,178), ZnAPO-59 (U.S. Pat. No. 8,871,177), ZnAPO-67(U.S. Pat. No. 8,697,927), and MeAPSO-64 (U.S. Pat. No. 8,696,886). Therelationship between the increasing product charge densities andreaction parameters, namely the ETMAOH(DEDMAOH)/H₃PO₄ ratios, wereoutlined in the literature (See Microporous and Mesoporous Materials,189, 2014, 49-63). The incorporation of M²⁺ observed in these systemswas such that for the formulation [M²⁺ _(x)Al_(1-x)PO₄]^(x−), x˜0.2-0.3.

Applicants have now synthesized a new family of highly chargedmetallophosphate framework materials, designated PST-19, with highercharge densities than the MeAPOs of U.S. Pat. No. 4,567,029 and theZnAPO materials isolated by Lewis. These metallophosphates are preparedfrom aqueous solution utilizing a combination quaternary ammonium andalkali cations. The PST-19 materials have the SBS topology (See Databaseof Zeolite Structures, www.iza-structure.org/databases) and have highermetal content than reported for the SBS topology material UCSB-6, inwhich the maximum metal incorporation observed was 45% replacement ofAl³⁺ with Co²⁺ (See Science, 1997, 278, 2080). Further distinguishingthis work from that of Stucky is that aqueous solutions are employedhere; free of ethylene glycol solvent and dipropylamine ordiisopropylamine co-solvents used in the synthesis of UCSB-6. Theapproach used here produces PST-19 crystals with micron to sub-microndimensions while the UCSB-6 materials exhibit gigantic crystaldimensions by comparison ranging from 150 to 600μ. The utility of alkaliin MeAPO-based systems is uncommon and in combination with quaternaryammonium cations under the right conditions enables this system toachieve the charge densities and desired midrange compositions betweenthe low charge density MeAPOs of U.S. Pat. No. 4,567,029 and high chargedensity M²⁺ phosphate extremes of Bedard and Gier.

SUMMARY OF THE INVENTION

As stated, the present invention relates to a new family ofmetallophosphate molecular sieves designated PST-19. Accordingly, oneembodiment of the invention is a microporous crystalline material havinga three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and anhydrous basis expressed by an empirical formulaof:

R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z)

where R is at least one quaternary ammonium cation selected from thegroup consisting of tetraethylammonium (TEA⁺), triethylpropylammonium(TEPA⁺), diethylmethylpropylammonium (DEMPA⁺),dimethylethylpropylammonium (DMEPA⁺), dimethyldipropylammonium (DMDPA⁺),methyltriethylammonium (MTEA⁺), ethyltrimethylammonium (ETMA⁺),diethyldimethylammonium (DEDMA⁺), choline, hexamethonium (HM²⁺),propyltrimethylammonium (PTMA⁺), butyltrimethylammonium (BTMA⁺),hexamethonium (HM²⁺), tetramethylammonium (TMA⁺), tetrapropylammonium(TPA⁺) and mixtures thereof, “r” is the mole ratio of R to P and has avalue of about 0.04 to about 1.0, “p” is the weighted average valence ofR and varies from 1 to 2, A is an alkali metal such as Li⁺, Na⁺, K⁺, Rb⁺and Cs⁺ and mixtures thereof, “m” is the mole ratio of A to P and variesfrom 0.1 to 1.0, M is a divalent element selected from the group of Zn,Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of M to P andvaries from 0.2 to about 0.9, E is a trivalent element selected from thegroup consisting of aluminum and gallium and mixtures thereof, “y” isthe mole ratio of E to P and varies from 0.1 to about 0.8 and “z” is themole ratio of O to P and has a value determined by the equation:

z=(m+p·r+2·x+3·y+5)/2

and is characterized in that it has the x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table A:

TABLE A 2Θ d(Å) I/I₀ % 6.01-5.72 14.70-15.45 w-m 6.80-6.37 12.98-13.87vs 10.22-9.94  8.65-8.89 w 12.22-11.87 7.24-7.45 w 13.30-12.99 6.65-6.81w 15.62-15.18 5.67-5.83 w 15.86-15.52 5.585-5.705 w 16.75-16.405.29-5.40 w 20.35-19.89 4.36-4.46 w-m 21.29-20.69 4.17-4.29 w22.09-21.77 4.02-4.08 w-m 24.30-23.84 3.66-3.73 w 37.12-25.43 2.42-3.50w-m 27.00-26.51 3.30-3.36 w-m 28.59-28.22 3.12-3.16 w-m 29.46-28.973.03-3.08 w-m 31.48-31.03 2.84-2.88 w-m 35.52-35.02 2.525-2.56  w

Another embodiment of the invention is a process for preparing thecrystalline metallophosphate molecular sieve described above. Theprocess comprises forming a reaction mixture containing reactive sourcesof R, A, M, E and P and heating the reaction mixture at a temperature ofabout 60° C. to about 200° C. for a time sufficient to form themolecular sieve, the reaction mixture having a composition expressed interms of mole ratios of the oxides of:

aR_(2/p)O:bA₂O:cMO:E₂O₃:dP₂O₅:eH₂O

where “a” has a value of about 2.1 to about 100, “b” has a value ofabout 0.1 to about 8.0, “c” has a value of about 0.25 to about 8, “d”has a value of about 1.69 to about 25, and “e” has a value from 30 to5000.

Yet another embodiment of the invention is a hydrocarbon conversionprocess using the above-described molecular sieve as a catalyst. Theprocess comprises contacting at least one hydrocarbon with the molecularsieve at conversion conditions to generate at least one convertedhydrocarbon.

Still another embodiment of the invention is a separation process usingthe crystalline PST-19 material. The process may involve separatingmixtures of molecular species or removing contaminants by contacting afluid with the PST-19 molecular sieve. Separation of molecular speciescan be based either on the molecular size (kinetic diameter) or on thedegree of polarity of the molecular species. Removing contaminants maybe by ion exchange with the molecular sieve.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE shows an analysis of the product by SEM.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared a family of high charge density crystallinemicroporous metallophosphate compositions with the SBS topology,designated PST-19. Compared to other early MeAPO materials, the PST-19family of materials contains more M²⁺ and exhibits high framework (FW)charge densities that, unlike the other MeAPOs, use of alkali cations inaddition to organoammonium ions to balance the FW charge. The instantmicroporous crystalline material (PST-19) has an empirical compositionin the as-synthesized form and on an anhydrous basis expressed by theempirical formula:

R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z)

where A is at least one alkali cation and is selected from the group ofalkali metals. Specific examples of the A cations include but are notlimited to lithium, sodium, potassium, rubidium, cesium and mixturesthereof. R is at least one quaternary ammonium cation, examples of whichinclude but are not limited to tetraethylammonium (TEA⁺),triethylpropylammonium (TEPA⁺), diethylmethylpropylammonium (DEMPA⁺),dimethylethylpropylammonium (DMEPA⁺), dimethyldipropylammonium (DMDPA⁺),methyltriethylammonium (MTEA⁺), ethyltrimethylammonium (ETMA⁺), choline,diethyldimethylammonium (DEDMA⁺), propyltrimethylammonium (PTMA⁺),butyltrimethylammonium (BTMA⁺), hexamethonium (HM²⁺),tetramethylammonium (TMA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, and “r” is the mole ratio of R to P and varies from about 0.04to about 1.0, while “p” is the weighted average valence of R and variesfrom about 1 to 2. M and E are tetrahedrally coordinated and in theframework, M is a divalent element selected from the group of Zn, Mg,

Co, Mn and mixtures thereof, while E is a trivalent element selectedfrom aluminum and gallium and mixtures thereof. In PST-19, it is alsopossible for a portion of M²⁺ to be located in the pore, balancing FWcharge. The value of “m” is the mole ratio of A to P and varies from 0.1to about 1.0, “x” is mole ratio of M to P and varies from 0.2 to about0.9, while the ratio of E to P is represented by “y” which varies fromabout 0.10 to about 0.8. Lastly, “z” is the mole ratio of 0 to P and isgiven by the equation:

z=(m+r·p+2·x+3·y+5)/2.

When only one type of R organoammonium cation is present, then theweighted average valence is just the valence of that cation, e.g., +1 or+2. When more than one R cation is present, the total amount of R isgiven by the equation:

R _(r) ^(p+) =R _(r1) ^((p1)+) +R _(r2) ^((p2)+) R _(r3) ^((p3)+) +. . .

the weighted average valence “p” is given by:

$p = \frac{{r\; {1 \cdot p}\; 1} + {r\; {2 \cdot p}\; 2} + {r\; {3 \cdot p}\; 3} + \ldots}{{r\; 1} + {r\; 2} + {r\; 3} + \ldots}$

It has also been noted that in the PST-19 materials of this inventionthat a portion of M²⁺ may also reside in the pores, likely in a chargebalancing role.

The microporous crystalline metallophosphate PST-19 is prepared by ahydrothermal crystallization of a reaction mixture prepared by combiningreactive sources of R, A, E, phosphorous and M. A preferred form of thePST-19 materials is when E is Al. The sources of aluminum include butare not limited to aluminum alkoxides, precipitated aluminas, aluminummetal, aluminum hydroxide, aluminum salts, alkali aluminates and aluminasols. Specific examples of aluminum alkoxides include, but are notlimited to aluminum tri- sec-butoxide and aluminum tri-isopropoxide.Sources of phosphorus include, but are not limited to, orthophosphoricacid, phosphorus pentoxide, and ammonium dihydrogen phosphate. Sourcesof M include but are not limited to zinc acetate, zinc chloride, cobaltacetate, cobalt chloride, magnesium acetate, magnesium nitrate,manganese sulfate, manganese acetate and manganese nitrate. Sources ofgallium, the other E element, include but are not limited toprecipitated gallium hydroxide, gallium chloride, gallium sulfate orgallium nitrate. Sources of the A metals include the halide salts,nitrate salts, hydroxide salts, acetate salts, and sulfate salts of therespective alkali metals. R is at least one quaternary ammonium cationselected from the group consisting of tetraethylammonium (TEA⁺),triethylpropylammonium (TEPA⁺), diethylmethylpropylammonium (DEMPA⁺),dimethylethylpropylammonium (DMEPA⁺), dimethyldipropylammonium (DMDPA⁺),methyltriethylammonium (MTEA⁺), ethyltrimethylammonium (ETMA⁺),diethyldimethylammonium (DEDMA⁺), choline, propyltrimethylammonium(PTMA⁺), butyltrimethylammonium (BTMA⁺), hexamethonium (HM²⁺),tetramethylammonium (TMA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, and the sources include the hydroxide, acetate, chloride,bromide, iodide and fluoride compounds. Specific examples includewithout limitation tetraethylammonium hydroxide, triethylpropylammoniumhydroxide, diethylmethylpropylammonium hydroxide,dimethylethylpropylammonium hydroxide, dimethyldipropylammoniumhydroxide, methyltriethylammonium hydroxide, hexamethonium dihydroxide,hexamethonium dichloride, choline hydroxide, choline chloride,propyltrimethylammonium hydroxide, propyltrimethylammonium chloride,tetrapropylammonium hydroxide and tetramethylammonium chloride. In oneembodiment R is TEA⁺. In another embodiment, R istriethylpropylammonium. In yet another embodiment, R isdimethylethylpropylammonium. In another embodiment, R isdiethylmethylpropylammonium. In yet another embodiment, R isdimethyldipropylammonium. Finally, in another embodiment, R ismethyltriethylammonium.

The reaction mixture containing reactive sources of the desiredcomponents can be described in terms of molar ratios of the oxides bythe formula:

aR_(2p)O:bA₂O:cMO:E₂O₃: dP₂O₅:eH₂O

where “a” varies from about 2.1 to about 100, “b” varies from about 0.1to about 8, “c” varies from about 0.25 to about 8, “d” varies from about1.69 to about 25, and “e’ varies from 30 to 5000. If alkoxides are used,it is preferred to include a distillation or evaporative step to removethe alcohol hydrolysis products. The reaction mixture is now reacted ata temperature of about 60° C. to about 200° C. and preferably from about95° C. to about 175° C. for a period of about 1 day to about 3 weeks andpreferably for a time of about 1 day to about 7 days in a sealedreaction vessel at autogenous pressure. After crystallization iscomplete, the solid product is isolated from the heterogeneous mixtureby means such as filtration or centrifugation, washed with de-ionizedwater and dried in air at ambient temperature up to about 100° C. PST-19seeds can optionally be added to the reaction mixture in order toaccelerate or otherwise enhance the formation of the desired microporouscomposition.

The PST-19 metallophosphate-based material, which is obtained from theabove-described process, is characterized by the powder x-raydiffraction pattern, having at least the d-spacings and relativeintensities set forth in Table A below.

TABLE A 2Θ d(Å) I/I₀ % 6.01-5.72 14.70-15.45 w-m 6.80-6.37 12.98-13.87vs 10.22-9.94  8.65-8.89 w 12.22-11.87 7.24-7.45 w 13.30-12.99 6.65-6.81w 15.62-15.18 5.67-5.83 w 15.86-15.52 5.585-5.705 w 16.75-16.405.29-5.40 w 20.35-19.89 4.36-4.46 w-m 21.29-20.69 4.17-4.29 w22.09-21.77 4.02-4.08 w-m 24.30-23.84 3.66-3.73 w 37.12-25.43 2.42-3.50w-m 27.00-26.51 3.30-3.36 w-m 28.59-28.22 3.12-3.16 w-m 29.46-28.973.03-3.08 w-m 31.48-31.03 2.84-2.88 w-m 35.52-35.02 2.525-2.56  w

The PST-19 may be modified in many ways to tailor it for use in aparticular application. Modifications include calcination, ammoniacalcinations, ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof, as outlinedfor the case of UZM-4 in U.S. Pat. No. 6,776,975 B1 which isincorporated by reference in its entirety. In addition, properties thatmay be modified include porosity, adsorption, framework composition,acidity, thermal stability, ion-exchange capacity, etc.

As synthesized, the PST-19 material will contain some of theexchangeable or charge balancing cations in its pores. Theseexchangeable cations can be exchanged for other cations, or in the caseof organic cations, they can be removed by heating under controlledconditions. Because PST-19 is a large pore material and the SBSstructure has a 3-dimensional 12-ring pore system as well as some 8-ringpores, many organic cations may be removed directly by ion-exchange andheating may not be necessary. If heating is necessary to remove theorganic cation from the pores, a preferred method is ammoniacalcination. Calcination in air converts the organic cations in thepores to protons, which can lead to the loss of some metal, for exampleAl, from the framework upon exposure to ambient atmospheric water vapor.When the calcination is carried out in an ammonia atmosphere, theorganic cation in the pore is replaced by NH₄ ⁺ cation and the frameworkremains intact (See Studies in Surface Science, (2004) vol. 154, p.1324-1331). Typical conditions for ammonia calcinations include the useof gaseous anhydrous ammonia flowing at a rate of 1.1 1/min whileramping the sample temperature at 5° C./min to 500° C. and holding atthat temperature for a time ranging from 5 minutes to an hour. Theresulting ammonium/alkali form of PST-19 has essentially the diffractionpattern of Table A. Once in this form, the ammonia calcined material maybe ion-exchanged with H⁺, NH₄ ⁺, alkali metals, alkaline earth metals,transition metals, rare earth metals, or any mixture thereof, to achievea wide variety of compositions with the PST-19 framework in superiorcondition.

When PST-19 or its modified forms are calcined in air, there can be aloss of metal from the framework, such as Al, which can alter the x-raydiffraction pattern from that observed for the as-synthesized PST-19(See Studies in Surface Science, (2004) vol. 154, p. 1324-1331).

Typical conditions for the calcination of the PST-19 sample includeramping the temperature from room temperature to a calcinationtemperature of 400-600° C., preferably a calcination temperature of450-550° C. at a ramp rate of 1 to 5° C./min, preferably a ramp rate of2 to 4° C./min, the temperature ramp conducted in an atmosphereconsisting either of flowing nitrogen or flowing clean dry air,preferably an atmosphere of flowing nitrogen. Once at the desiredcalcination temperature, if the calcination atmosphere employed duringthe temperature ramp is flowing clean dry air, it may remain flowingclean dry air. If the calcination atmosphere during the ramp was flowingnitrogen, it may remain flowing nitrogen at the calcination temperatureor it may be immediately converted to clean dry air; preferably at thecalcination temperature the calcination atmosphere will remain flowingnitrogen for a period of 1-10 hr and preferably for a period of 2-4hours before converting the calcination atmosphere to flowing clean dryair. The final step of the calcination is a dwell at the calcinationtemperature in flowing clean dry air. Whether the calcination atmosphereduring the initial temperature ramp was flowing nitrogen or flowingclean dry air, once at the calcination temperature and once thecalcination atmosphere is flowing clean dry air, the PST-19 sample willspend a period of 1-24 hr and preferably a period of 2-6 hr under theseconditions to complete the calcination process.

The crystalline PST-19 materials of this invention can be used forseparating mixtures of molecular species, removing contaminants throughion exchange and catalyzing various hydrocarbon conversion processes.Separation of molecular species can be based either on the molecularsize (kinetic diameter) or on the degree of polarity of the molecularspecies.

The PST-19 compositions of this invention can also be used as a catalystor catalyst support in various hydrocarbon conversion processes.Hydrocarbon conversion processes are well known in the art and includecracking, hydrocracking, alkylation of both aromatics and isoparaffin,isomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydration, dehydration,hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanol toolefins, methanation and syngas shift process. Specific reactionconditions and the types of feeds which can be used in these processesare set forth in U.S. Pat. Nos. 4,310,440, 4,440,871 and 5,126,308,which are incorporated by reference. Preferred hydrocarbon conversionprocesses are those in which hydrogen is a component such ashydrotreating or hydrofining, hydrogenation, hydrocracking,hydrodenitrogenation, hydrodesulfurization, etc.

Hydrocracking conditions typically include a temperature in the range of400° to 1200° F. (204-649° C.), preferably between 600° and 950° F.(316-510° C.). Reaction pressures are in the range of atmospheric toabout 3,500 psig (24,132 kPa g), preferably between 200 and 3000 psig(1379-20,685 kPa g). Contact times usually correspond to liquid hourlyspace velocities (LHSV) in the range of about 0.1 hr⁻¹ to 15 hr⁻¹,preferably between about 0.2 and 3 hr⁻¹. Hydrogen circulation rates arein the range of 1,000 to 50,000 standard cubic feet (scf) per barrel ofcharge (178-8,888 std. m³/m³), preferably between 2,000 and 30,000 scfper barrel of charge (355-5,333 std. m³/m³). Suitable hydrotreatingconditions are generally within the broad ranges of hydrocrackingconditions set out above.

The reaction zone effluent is normally removed from the catalyst bed,subjected to partial condensation and vapor-liquid separation and thenfractionated to recover the various components thereof. The hydrogen,and if desired some or all of the unconverted heavier materials, arerecycled to the reactor. Alternatively, a two-stage flow may be employedwith the unconverted material being passed into a second reactor.Catalysts of the subject invention may be used in just one stage of sucha process or may be used in both reactor stages.

Catalytic cracking processes are preferably carried out with the PST-19composition using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residua, etc. with gasoline being the principaldesired product. Temperature conditions of 850° to 1100° F. (455° C. to593° C.), LHSV values of 0.5 hr⁻¹ to 10 hr⁻¹ and pressure conditions offrom about 0 to 50 psig (0-345 kPa) are suitable.

Alkylation of aromatics usually involves reacting an aromatic (C₂ toC₁₂), especially benzene, with a monoolefin to produce a linear alkylsubstituted aromatic. The process is carried out at an aromatic:olefin(e.g., benzene:olefin) ratio of between 5:1 and 30:1, a LHSV of about0.3 to about 6 hr⁻¹, a temperature of about 100° to about 250° C. andpressures of about 200 to about 1000 psig (1,379-6,895 kPa). Furtherdetails on apparatus may be found in U.S. Pat. No. 4,870,222 which isincorporated by reference.

Alkylation of isoparaffins with olefins to produce alkylates suitable asmotor fuel components is carried out at temperatures of −30° to 40° C.,pressures from about atmospheric to about 6,894 kPa (1,000 psig) and aweight hourly space velocity (WHSV) of 0.1 hr⁻¹ to about 120 hr⁻¹.Details on paraffin alkylation may be found in U.S. Pat. Nos. 5,157,196and 5,157,197, which are incorporated by reference.

The conversion of methanol to olefins is effected by contacting themethanol with the PST-19 catalyst at conversion conditions, therebyforming the desired olefins. The methanol can be in the liquid or vaporphase with the vapor phase being preferred. Contacting the methanol withthe PST-19 catalyst can be done in a continuous mode or a batch modewith a continuous mode being preferred. The amount of time that themethanol is in contact with the PST-19 catalyst must be sufficient toconvert the methanol to the desired light olefin products. When theprocess is carried out in a batch process, the contact time varies fromabout 0.001 hrs to about 1 hr and preferably from about 0.01 hr toabout 1. 0 hr. The longer contact times are used at lower temperatureswhile shorter times are used at higher temperatures. Further, when theprocess is carried out in a continuous mode, the Weight Hourly SpaceVelocity (WHSV) based on methanol can vary from about 1 hr⁻¹ to about1000 hr⁻¹ and preferably from about 1 hr⁻¹ to about 100 hr⁻¹.

Generally, the process must be carried out at elevated temperatures inorder to form light olefins at a fast enough rate. Thus, the processshould be carried out at a temperature of about 300° C. to about 600°C., preferably from about 400° C. to about 550° C. and most preferablyfrom about 450° C. to about 525° C. The process may be carried out overa wide range of pressure including autogenous pressure. Thus, thepressure can vary from about 0 kPa (0 psig) to about 1724 kPa (250 psig)and preferably from about 34 kPa (5 psig) to about 345 kPa (50 psig).

Optionally, the methanol feedstock may be diluted with an inert diluentin order to more efficiently convert the methanol to olefins. Examplesof the diluents which may be used are helium, argon, nitrogen, carbonmonoxide, carbon dioxide, hydrogen, steam, paraffinic hydrocarbons, e.g., methane, aromatic hydrocarbons, e. g., benzene, toluene and mixturesthereof. The amount of diluent used can vary considerably and is usuallyfrom about 5 to about 90 mole percent of the feedstock and preferablyfrom about 25 to about 75 mole percent.

The actual configuration of the reaction zone may be any well-knowncatalyst reaction apparatus known in the art. Thus, a single reactionzone or a number of zones arranged in series or parallel may be used. Insuch reaction zones the methanol feedstock is flowed through a bedcontaining the PST-19 catalyst. When multiple reaction zones are used,one or more PST-19 catalysts may be used in series to produce thedesired product mixture. Instead of a fixed bed, a dynamic bed system,e. g., fluidized or moving, may be used. Such a dynamic system wouldfacilitate any regeneration of the PST-19 catalyst that may be required.If regeneration is required, the PST-19 catalyst can be continuouslyintroduced as a moving bed to a regeneration zone where it can beregenerated by means such as oxidation in an oxygen containingatmosphere to remove carbonaceous materials.

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims. The products of thisinvention are designated with the general name PST-19, with theunderstanding that all of the PST-19 materials exhibit a structure withthe SBS topology.

The structure of the PST-19 compositions of this invention wasdetermined by x-ray analysis. The x-ray patterns presented in thefollowing examples were obtained using standard x-ray powder diffractiontechniques. The radiation source was a high-intensity, x-ray tubeoperated at 45 kV and 35 mA. The diffraction pattern from the copperK-alpha radiation was obtained by appropriate computer based techniques.Flat compressed powder samples were continuously scanned at 2° to 56°(2θ). Interplanar spacings (d) in Angstrom units were obtained from theposition of the diffraction peaks expressed as θ where θ is the Braggangle as observed from digitized data. Intensities were determined fromthe integrated area of diffraction peaks after subtracting background,“I_(o)” being the intensity of the strongest line or peak, and “I” beingthe intensity of each of the other peaks.

As will be understood by those skilled in the art the determination ofthe parameter 20 is subject to both human and mechanical error, which incombination can impose an uncertainty of about ±0.4° on each reportedvalue of 2θ. This uncertainty is, of course, also manifested in thereported values of the d-spacings, which are calculated from the 2θvalues. This imprecision is general throughout the art and is notsufficient to preclude the differentiation of the present crystallinematerials from each other and from the compositions of the prior art. Insome of the x-ray patterns reported, the relative intensities of thed-spacings are indicated by the notations vs, s, m, and w whichrepresent very strong, strong, medium, and weak, respectively. In termsof 100×I/I_(o), the above designations are defined as:

w=0-15; m=15-60: s=60-80 and vs=80-100

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present.

In order to more fully illustrate the invention, the following examplesare set forth. It is to be understood that the examples are only by wayof illustration and are not intended as an undue limitation on the broadscope of the invention as set forth in the appended claims.

EXAMPLE 1

A Teflon beaker was charged with 120.00g tetraethylammonium hydroxide(TEAOH, 35%), SACHEM Inc.) and placed under a high speed overheadstirrer. Pre-ground aluminum isopropoxide (13.3% Al, Sigma-Aldrich),5.79 g, was dissolved in the TEAOH solution. This was followed by thefast dropwise addition of 19.57 g H₃PO₄ (85.7%). The reaction mixturewas diluted with 37.65 g de-ionized water. Separately, a zinc acetatesolution was prepared by dissolving 6.26 g Zn(OAc)₂*2H₂O in 35.00 gde-ionized water. This solution was added in a fast dropwise manner tothe reaction mixture with vigorous stirring. Then a solution wasprepared by dissolving 1.41 g potassium acetate, KOAc (99.4%), in 25.00g de-ionized water. This solution was also added fast dropwise to thereaction mixture, resulting in a clear solution. The reaction mixturewas distributed among 7 Teflon-lined autoclaves which were digestedquiescently at 95, 125, 150 and 175° C. for either 59 or 159 hr or bothat autogenous pressure. The solid products were isolated bycentrifugation, washed with de-ionized water and dried at roomtemperature. The major product in every case was determined to be PST-19by x-ray powder diffraction, with most of the reactions yieldingproducts showing no impurities. Representative x-ray diffraction linesare listed for the PST-19 product resulting from the 125° C./159 hrreaction in table 1 below. Analysis by Scanning Electron Microscopy(SEM) showed the PST-19 product to consist of extremely thin platecrystals, with the plate face diameters ranging from about 0.3 to about1 across while plate thicknesses are on the order of 0.01 to about 0.1μ.Elemental analysis yielded the stoichiometryTEA_(0.05)K0.33Al_(0.51)Zn_(0.62)P for the PST-19 product.

TABLE 1 2-Θ d(Å) I/I₀(%) 5.78 15.28 w 6.50 13.59 vs 10.00 8.83 w 11.947.40 w 13.14 6.73 w 15.32 5.78 w 15.60 5.68 w 16.53 5.36 w 20.04 4.43 m20.94 4.24 w 21.98 4.04 m 22.14 4.01 w 23.98 3.71 w 25.78 3.45 w 26.663.34 m 27.78 3.21 w 28.24 3.16 m 29.14 3.06 w 31.20 2.86 m 35.20 2.55 w

EXAMPLE 2

A Teflon beaker was charged with 928.44 g of Triethylpropylammoniumhydroxide (TEPAOH, 19.7%, SACHEM Inc.) followed by the addition 27.96 gof aluminum tri-sec-butoxide (Sigma Aldrich, 97+%), which were thenhomogenized with a high speed overhead stirrer to make a clear solution.Then 78.50 g of H₃PO₄ (85%) was slowly added to the mixture. Separately,24.91 g of Zn(OAc)₂*2H₂O was dissolved in 60 g de-ionized water and thenwas added dropwise to the reaction mixture with vigorous mixing.Similarly, 2.12 g of KCl was dissolved in 10.00 g de-ionized water andadded dropwise to the stirring reaction mixture. The reaction mixturewas further homogenized until it was a clear solution. A portion of thesolution, 1050 g, was placed in a 2-L Teflon-lined PARR reactor anddigested quiescently for 92 hours at 175° C. at autogenous pressure. Thesolid product was isolated by centrifugation, washed with de-ionizedwater and dried at room temperature. Characterization via powder x-raydiffraction showed that the product was PST-19 with the SBS topology.Representative diffraction lines observed for the product are providedbelow in table 2. FIG. 1 shows that analysis by SEM showed the productto consist of hexagonal plate crystals with dimensions across the faceof the plate ranging from 0.2 to about 2μ, while the plate thickness isless than about 0.1μ. Elemental analysis yielded the stoichiometryTEPA_(0.18)K_(0.22)Zn_(0.63)Al_(0.43)P for the PST-19 product.

TABLE 2 2-Θ d(Å) I/I₀(%) 5.92 14.93 w 6.69 13.20 vs 10.15 8.71 w 11.407.76 w 11.68 7.57 w 12.10 7.31 w 13.22 6.69 w 15.43 5.74 w 15.77 5.61 w16.62 5.33 w 18.70 4.74 w 20.22 4.39 w 21.06 4.22 w 21.97 4.04 w 22.214.00 w 24.13 3.69 w 25.71 3.46 w 25.85 3.44 w 26.46 3.37 w 26.77 3.33 w28.38 3.14 w 29.29 3.05 w 29.92 2.98 w 30.44 2.93 w 31.35 2.85 w 32.832.73 w 35.32 2.54 w

EXAMPLE 3

A Teflon beaker was charged with 81.72 g of Diethylmethylpropylammoniumhydroxide (DEMPAOH, 20.7% , SACHEM Inc.) followed by the addition of2.83 g of aluminum-tri-sec-butoxide (97+%), which were then homogenizedwith a high speed overhead stirrer to make a clear solution. Then 7.96 gof H₃PO₄ (85%) was slowly added to the mixture as stirring continued.Separately, 2.53 g of Zn(OAc)₂*2H₂O was dissolved in 8.00 g de-ionizedwater. This solution was added to the reaction mixture in a dropwisefashion. Next, a solution was prepared by dissolving 0.43 g KCl in 4.00g de-ionized water. This solution was also added dropwise to thereaction mixture with vigorous stirring. The resulting clear solutionwas distributed among three Teflon-lined autoclaves that were digestedfor 48, 72, and 96 hr at 175° C., rotated in a rotisserie oven atautogenous pressure. The products were isolated by centrifugation,washed with de-ionized water, and dried at 100° C. The products wereidentified as PST-19 with the SBS topology by powder x-ray diffraction.Representative diffraction lines are shown for the products in Table 3A(48 hr product) and Table 3B (96 hr product). Elemental analysis on theproduct from the 48 hr digestion yielded the stoichiometryDEMPA_(0.19)K_(0.26)Al_(0.45)Zn_(0.57)P for the PST-19 product.

TABLE 3 Table 3A Table 3B 2-Θ d(Å) I/I₀(%) 2-Θ d(Å) I/I₀(%) 5.85 15.09 w5.93 14.88 w 6.51 13.56 vs 6.63 13.32 vs 10.08 8.77 w 10.13 8.73 w 11.667.58 w 11.71 7.55 w 12.02 7.36 w 12.11 7.30 w 13.08 6.77 w 13.20 6.70 w15.37 5.76 w 15.49 5.72 w 15.69 5.64 w 15.75 5.62 w 16.49 5.37 w 16.615.33 w 18.64 4.76 w 18.70 4.74 w 20.14 4.41 w 20.22 4.39 w 20.46 4.34 w21.11 4.20 w 21.00 4.23 w 21.95 4.05 w 21.94 4.05 w 24.15 3.68 w 24.053.70 w 25.84 3.44 w 25.67 3.47 w 26.40 3.37 w 26.34 3.38 w 26.82 3.32 w26.72 3.33 w 27.66 3.22 w 27.72 3.22 w 28.34 3.15 w 28.22 3.16 w 29.303.05 w 29.22 3.05 w 29.91 2.98 w 29.84 2.99 w 30.47 2.93 w 30.45 2.93 w31.33 2.85 w 31.23 2.86 w 35.34 2.54 w 35.22 2.55 w

EXAMPLE 4

A Teflon beaker was charged with 77.36 g of dimethylethylpropylammoniumhydroxide (DMEPAOH, SACHEM Inc., 20.0%) and placed under a high-speedoverhead stirrer. Then 2.87 g aluminum tri-sec-butoxide (97+%) was addedwith stirring, easily dissolving within minutes. This was followed bythe dropwise addition of 8.05 g of H₃PO₄ (85%). Separately,Zn(OAc)₂*2H₂O, 2.55 g, was dissolved in 8.00 g de-ionized water. Thissolution was added drop-wise to the stirring reaction mixture. Next,KCl, 0.43 g, was dissolved in 4.00 g de-ionized water and added dropwisewith continued stirring. Continued homogenization of the reactionmixture produced a clear solution. The final reaction mixture wasdistributed among (3) Teflon-lined autoclaves and digested for periodsof 48, 72 and 96 hr at 175° C., rotated in a rotisserie oven atautogenous pressure. The products were isolated by centrifugation,washed with de-ionized water and dried at 100° C. The products wereidentified as PST-19 with the SBS topology via powder x-ray diffraction.Representative diffraction lines are given for the products from the 48and 96 hr digestions in Tables 4A and 4B, respectively. Elementalanalysis on the product digested for 48 hr yielded the stoichiometryDMEPA_(0.20)K_(0.31)Zn_(0.58)Al_(0.44)P for the PST-19 product.

TABLE 4 Table 4A Table 4B 2-Θ d(Å) I/I₀(%) 2-Θ d(Å) I/I₀(%) 5.81 15.20 w5.89 14.99 m 6.47 13.65 vs 6.55 13.48 vs 10.01 8.83 w 10.12 8.73 w 11.617.61 w 11.66 7.58 w 11.96 7.40 w 12.04 7.35 w 13.10 6.76 w 13.08 6.77 w15.31 5.78 w 13.41 6.60 w 15.65 5.66 w 15.41 5.75 w 16.51 5.37 w 15.775.62 w 18.60 4.77 w 16.59 5.34 w 20.08 4.42 w 18.68 4.75 w 20.80 4.27 w20.18 4.40 w 21.99 4.04 w 20.61 4.31 w 23.21 3.83 w 21.02 4.22 w 23.973.71 w 21.88 4.06 w 25.58 3.48 w 24.11 3.69 w 26.78 3.33 w 25.67 3.47 w28.18 3.16 w 26.80 3.32 w 29.17 3.06 w 27.64 3.22 w 31.17 2.87 w 28.323.15 w 35.24 2.54 w 29.26 3.05 w 30.39 2.94 w 31.15 2.87 w 31.37 2.85 w32.83 2.73 w 34.76 2.58 w 35.23 2.55 w

1. A microporous crystalline metallophosphate material having athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [E_(4/2)]⁻ and[PO_(4/2)]⁺ and tetrahedral units and an empirical composition in the assynthesized form and on an anhydrous basis expressed by an empiricalformula of:R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternaryammonium cation selected from the group consisting of tetraethylammonium(TEA⁺), triethylpropylammonium (TEPA⁺), diethylmethylpropylammonium(DEMPA⁺), dimethylethylpropylammonium (DMEPA⁺), dimethyldipropylammonium(DMDPA⁺), methyltriethylammonium (MTEA⁺), ethyltrimethylammonium(ETMA⁺), diethyldimethylammonium (DEDMA⁺), choline, hexamethonium(HM²⁺), propyltrimethylammonium (PTMA⁺), butyltrimethylammonium (BTMA⁺),hexamethonium (HM²⁺), tetramethylammonium (TMA⁺), tetrapropylammonium(TPA⁺) and mixtures thereof, “r” is the mole ratio of R to P and has avalue of about 0.04 to about 1.0, “p” is the weighted average valence ofR and varies from 1 to 2, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is themole ratio of A to P and varies from 0.1 to 1.0, M is a divalent elementselected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” isthe mole ratio of M to P and varies from 0.2 to about 0.9, E is atrivalent element selected from the group consisting of aluminum andgallium and mixtures thereof, “y” is the mole ratio of E to P and variesfrom 0.1 to about 0.8 and “z” is the mole ratio of O to P and has avalue determined by the equation:z=(m+p·r+2·x+3·y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2Θ d(Å) I/I₀ % 6.01-5.72 14.70-15.45 w-m6.80-6.37 12.98-13.87 vs 10.22-9.94  8.65-8.89 w 12.22-11.87 7.24-7.45 w13.30-12.99 6.65-6.81 w 15.62-15.18 5.67-5.83 w 15.86-15.52 5.585-5.705w 16.75-16.40 5.29-5.40 w 20.35-19.89 4.36-4.46 w-m 21.29-20.694.17-4.29 w 22.09-21.77 4.02-4.08 w-m 24.30-23.84 3.66-3.73 w37.12-25.43 2.42-3.50 w-m 27.00-26.51 3.30-3.36 w-m 28.59-28.223.12-3.16 w-m 29.46-28.97 3.03-3.08 w-m 31.48-31.03 2.84-2.88 w-m35.52-35.02 2.525-2.56  w

wherein the crystalline microporous metallophosphate is modified by aprocess selected from the group consisting of calcination, ammoniacalcinations, ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof.
 2. Themetallophosphate material of claim 1 where E is aluminum.
 3. Themetallophosphate material of claim 1 where R is tetraethylammoniumcation, TEA⁺.
 4. The metallophosphate material of claim 1 where R is thetriethylpropylammonium cation, TEPA⁺.
 5. The metallophosphate materialof claim 1 where R is the diethylmethylpropylammonium cation, DEMPA⁺. 6.The metallophosphate material of claim 1 where R is thedimethylethylpropylammonium cation, DMEPA⁺.
 7. The metallophosphatematerial of claim 1 where R is the methyltriethylammonium cation, MTEA⁺.8. The metallophosphate material of claim 1 where R is thedimethyldipropylammonium cation, DMDPA⁺.
 9. The metallophosphatematerial of claim 1 with crystal dimensions less than about 5 micronsand preferably less than 3 microns and more preferably less than 2microns.
 10. A process of contacting a feed with a crystallinemicroporous PST-19 material wherein the process is a hydrocarbonconversion process or a separation process wherein the hydrocarbonconversion process comprises contacting a hydrocarbon stream with acatalyst at hydrocarbon conversion conditions to generate at least oneconverted product, wherein the catalyst is selected from the groupconsisting of a crystalline microporous PST-19 material, a modifiedcrystalline microporous PST-19 material and mixtures thereof, wherePST-19 is a crystalline microporous metallophosphate having athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and on an anhydrous basis expressed by an empiricalformula of:R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternaryammonium cation selected from the group consisting of tetraethylammonium(TEA⁺), triethylpropylammonium (TEPA⁺), diethylmethylpropylammonium(DEMPA⁺), dimethylethylpropylammonium (DMEPA⁺), dimethyldipropylammonium(DMDPA⁺), methyltriethylammonium (MTEA⁺), ethyltrimethylammonium(ETMA⁺), diethyldimethylammonium (DEDMA⁺), choline, hexamethonium(HM²⁺), propyltrimethylammonium (PTMA⁺), butyltrimethylammonium (BTMA⁺),hexamethonium (HM²⁺), tetramethylammonium (TMA⁺), tetrapropylammonium(TPA⁺) and mixtures thereof, “r” is the mole ratio of R to P and has avalue of about 0.04 to about 1.0, “p” is the weighted average valence ofR and varies from 1 to 2, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺and Cs⁺and mixtures thereof, “m” is themole ratio of A to P and varies from 0.1 to 1.0, M is a divalent elementselected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” isthe mole ratio of M to P and varies from 0.2 to about 0.9, E is atrivalent element selected from the group consisting of aluminum andgallium and mixtures thereof, “y” is the mole ratio of E to P and variesfrom 0.1 to about 0.8 and “z” is the mole ratio of 0 to P and has avalue determined by the equation:z=(m+p·r+2·x+3·y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2Θ d(Å) I/I₀ % 6.01-5.72 14.70-15.45 w-m6.80-6.37 12.98-13.87 vs 10.22-9.94  8.65-8.89 w 12.22-11.87 7.24-7.45 w13.30-12.99 6.65-6.81 w 15.62-15.18 5.67-5.83 w 15.86-15.52 5.585-5.705w 16.75-16.40 5.29-5.40 w 20.35-19.89 4.36-4.46 w-m 21.29-20.694.17-4.29 w 22.09-21.77 4.02-4.08 w-m 24.30-23.84 3.66-3.73 w37.12-25.43 2.42-3.50 w-m 27.00-26.51 3.30-3.36 w-m 28.59-28.223.12-3.16 w-m 29.46-28.97 3.03-3.08 w-m 31.48-31.03 2.84-2.88 w-m35.52-35.02 2.525-2.56  w

and the modified crystalline microporous PST-19 consists of athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units derived from PST-19 via the modificationprocesses of calcination, ammonia calcinations, ion-exchange, steaming,various acid extractions, ammonium hexafluorosilicate treatment, or anycombination thereof and wherein the separation process comprisescontacting at least two components with the catalyst to generate atleast one separated component.
 11. The process of claim 10 wherein thehydrocarbon conversion process is selected from the group consisting ofcracking, hydrocracking, alkylation, isomerization, polymerization,reforming, hydrogenation, dehydrogenation, transalkylation,dealkylation, hydration, dehydration, hydrotreating, hydrofining,hydrodenitrogenation, hydrodesulfurization, methanol to olefins,methanation, syngas shift process, olefin dimerization, oligomerization,dewaxing, and combinations thereof.
 12. The process of claim 10 whereinthe separation is based on molecular size of the components, degree ofpolarity of the components, or ion exchange of the components with thematerial.